EP3430085A1 - Matériaux pour encapsulation de del - Google Patents

Matériaux pour encapsulation de del

Info

Publication number
EP3430085A1
EP3430085A1 EP17713175.2A EP17713175A EP3430085A1 EP 3430085 A1 EP3430085 A1 EP 3430085A1 EP 17713175 A EP17713175 A EP 17713175A EP 3430085 A1 EP3430085 A1 EP 3430085A1
Authority
EP
European Patent Office
Prior art keywords
groups
silane
composite material
composite
silanes
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP17713175.2A
Other languages
German (de)
English (en)
Other versions
EP3430085B1 (fr
Inventor
Gerhard Domann
Daniela COLLIN
Carola CRONAUER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Ams Osram International GmbH
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Osram Opto Semiconductors GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV, Osram Opto Semiconductors GmbH filed Critical Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Publication of EP3430085A1 publication Critical patent/EP3430085A1/fr
Application granted granted Critical
Publication of EP3430085B1 publication Critical patent/EP3430085B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/483—Containers
    • H01L33/486—Containers adapted for surface mounting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/50—Wavelength conversion elements
    • H01L33/501—Wavelength conversion elements characterised by the materials, e.g. binder

Definitions

  • the present invention relates to a composite which is mainly suitable as an encapsulating material of LEDs and a matrix, embedded in the matrix particles and a
  • Dispersing agent wherein the dispersant envelops the dispersed in the matrix particles.
  • a common problem in LED applications is the low light extraction efficiency (LEE) of the semiconductor light source. This is partly due to the high refractive index difference between the semiconductor materials of the LED chip and the air surrounding the LED. Due to this difference, a large part of the emitted light is internally reflected by total reflection and not emitted as desired. This reduces the brightness and efficiency of the LED. Another undesirable consequence of the trapped light can be an increased heat generation, which also reduces the coupling-out efficiency, also referred to as conversion efficiency, and can lead to an increased degradation of the component (reduced device reliability). It is also desirable to be able to convert the light emerging from the LED, which is often blue or cold-colored, into warmer, longer-wavelength light.
  • the LED chip is often encapsulated with an encapsulating material.
  • Encapsulating materials are heretofore epoxy- or silicone-based systems.
  • the advantages of epoxy-based resins are above all the good adhesion of the material to the housing materials, the high transparency, the relatively high refractive indices and the low costs. This makes them well suited for low energy LEDs.
  • silicones are more expensive and often have a slightly lower refractive index compared to the epoxy systems; However, they usually have a higher thermal stability, which is why they are also used more often in high-energy LEDs applications.
  • High-indexing silicones achieve refractive indices of about 1.45 to about 1.54 or 1.55. However, these refractive indices are still significantly lower than the refractive indices of the emitting one
  • High-index, transparent and thermally and light-stable stable materials are needed as encapsulation materials for other technical areas, for example in OLED application, in photovoltaic applications, in projectors in the display industry and in all optical and opto-electronic systems, where higher temperatures ( eg> 150 ° C continuous load) or high optical powers are used (for example> 40 mW / cm 2 @ 405 nm). Also in these areas the achievement is as high as possible
  • Refractive index of the materials desirable is hitherto for example caused by the addition of molecular inorganic components, especially of (transition) metal compounds, since these often have a high refractive index.
  • the refractive index of the matrix by the incorporation of, for example, titanium (IV) or zirconium (IV) compounds at the molecular level (see, for example, Y. Lai, "Highly transparent thermal stable silicone / titanium hybrid with high refractive index for LED Encapsulation ", J. Coat. Technol. Res.
  • the refractive index of the encapsulation material can also be increased by the addition of inorganic nanoparticles (for example, oxides or sulfides) can be increased.
  • inorganic nanoparticles For example, oxides or sulfides
  • the prerequisite for this is that the size of the nanoparticles is significantly below the wavelength of the corresponding light in order to avoid scattering processes as much as possible. The scattering behavior and the
  • Refractive index enhancement are two complementary potential properties of nanoparticles in the encapsulation matrix (composite system).
  • a high-index hardcoat also based on polysiloxane, is presented, whose refractive index can be further increased by the addition of nanoparticles.
  • the polysiloxanes are crosslinked via typical crosslinking reactions (e.g., methacrylate or epoxy polymerization).
  • US 2010/025724 A1 describes a high-index, three-dimensionally crosslinked polysiloxane as an encapsulation material for LEDs.
  • the syntheses of this material are non-hydrolytic, ie without additional water addition for the hydrolysis reaction during the build-up of the inorganic network. This is achieved by the use of silanols as a necessary component.
  • the stochiometry ie the possible molar ratio between additionally organically crosslinkable silicon-containing components and aromatic silicon-containing components which are intended to increase the refractive index of the resin, is limited to a quasi-stoichiometric ratio between silanol and alkoxysilane groups.
  • High stability can be achieved by targeted and optimized nanoparticle syntheses and, if necessary, by subsequent surface functionalization.
  • hydrothermal or solvothermal synthetic routes e.g., as described in S. Zhou, "Dispersion Behavior of Zirconia Nanocrystals and Their Surface Functionalization with Vinyl Group-Containing Ligands", Langmuir 2007, 23, 9178
  • NP nanoparticles
  • matrix can be achieved by functionalizing the surfaces of NPs with organic groups. This succeeds in particular when the nanoparticles are metal oxide particles.
  • This functionalization has, as already mentioned, on the one hand a stabilization of the individual particles by steric (or electronic) shielding result.
  • functional groups may also be introduced to match the polarity of the inorganic oxide particles with those of the organic or hybrid matrix.
  • reactive groups can be integrated in this way, which allow a direct covalent attachment of the particles to the matrix in the final curing, whereby the
  • Alkoxysilane-functionalized metal oxide particles such as Zr0 2 nanoparticles for incorporation into silicone, acrylate or epoxy resins (see, for example, US 2009/140284 A), epoxy- and / or methacrylate-functionalized Zr0 2 nanoparticles for incorporation into epoxy resins as described by PT Chung in "Zr0 2 / epoxy nanocomposite for LED encapsulation", Mater. Chem. Phys. 2012, 136, 868 and isopropanol-functionalized TiO 2 particles for use in a silicone resin, see eg C.-C. Tuan, "Ultra High Refractive Indices LED Encapsulant", IEEE Electronic Components & Technology Conference 2014, 447.
  • Surface functionalization is not limited to the use of a single component. Rather, you can also different surface modifiers are used together. In all variants presented, it should be noted that a subsequent surface functionalization can contribute massively to the yellowing property.
  • Compatibility requires that the polarity between the particles and the matrix be adjusted for each matrix material.
  • An incorporation often fails if, for specific matrix materials which do not possess the typical functional groups such as methacrylate, acrylate, styryl, epoxy or amino functions or are not crosslinked by typical crosslinking reactions such as free-radical or cationic polymerization, no suitable functional Groups for functionalization can be found.
  • encapsulants for LEDs often requires processability of the material in the form of thick layers (e.g., in the form of lenses about 1 mm thick). If a high number of crosslinking groups is present, curing of the material in the form of thick layers (e.g., in the form of lenses about 1 mm thick). If a high number of crosslinking groups is present, curing of the material in the form of thick layers (e.g., in the form of lenses about 1 mm thick). If a high number of crosslinking groups is present, curing of the
  • Network formation e.g. (Meth) acrylates, epoxides, styryl groups and the like.
  • the susceptibility to cracking of the material must be reduced or optimized. This can be achieved by adjusting the number of reactive groups or the incorporation of flexible and long-chain molecular
  • Encapsulating materials which are composed of chain-shaped dimethyl / methylphenyl polysiloxanes and can be cured by means of UV exposure.
  • the end-group-functionalized polysiloxane chains allow the processing as a thick layer due to the relatively low proportion of reactive groups in comparison to the inorganic
  • Polysiloxanes also synthesize by the use of Tnalkoxysilanen whose polymeric structure is based less on the formation of chains, but much more of three-dimensional inorganic-crosslinked oligomers.
  • precursors having reactive organic functional groups such oligomers, whose inorganic network has been obtained by hydrolysis and condensation, carry the reactive groups on the Surface, whereby a strong three-dimensional organic crosslinking in the curing step can be achieved.
  • Both the authors of US 2010/025724 A1 and WO 2012/097836 A1 report on this material class.
  • the organic crosslinking and therefore also the number of reactive groups must be controlled in order to avoid cracking at high layer thicknesses.
  • a high proportion of aromatic groups such as phenyl groups which is highly desirable for achieving a high refractive index of the system, is beneficial in preventing cracking since they are not amenable to cross-linking and therefore tend to make the matrix material soft and flexible.
  • the thermal stability of the encapsulating material while irradiating with intense light output is another challenge.
  • silicones are significantly more stable than epoxy-based resins. Especially when using low-phenyl silicones a high yellowing stability is achieved.
  • a disadvantage of using phenyl-poor silicones is that in the substitution of the phenyl by methyl groups, the refractive index of the silicone matrix is significantly reduced (the refractive index of methyl silicones is about 1 .41, that of phenyl silicones at about 1 .53- 1 .54). In such a thermally and against UV irradiation stable, thereby however
  • a high proportion of aromatic groups such as phenyl groups is associated with the disadvantage that, in addition to inorganic crosslinking, organic crosslinking hardly takes place any more can.
  • organic crosslinking hardly takes place any more can.
  • a hydrolytic condensation ie, for example in the form of alkoxy groups
  • the phenyl groups are not available for organic crosslinking, as they differ from, for example Styryl groups have no organic polymerizable radicals. This reduces the possibility of curing the material sufficiently.
  • a composite material uncured
  • a composite (cured) comprising a polysiloxane-containing matrix, a dispersant and
  • Refractive index and a higher surface tension than the dispersing agent is constructed using at least two different silanes and aromatic groups and organic groups, the latter being bridged together via a bridging agent, wherein both the aromatic groups and the organic, bridgeable groups each above Carbon to a
  • Silicon matrix wherein the matrix additionally comprises a bridging agent for bridging the organobreakable groups and, if necessary, one for the
  • Dispersants were mixed and the resulting mixture with the
  • polysiloxane-containing matrix was combined, with the proviso that there are no styryl groups among the aromatic groups of the composite, or that the proportion of styryl groups at less than 5 mol%, preferably less than 1 mol%, based on the total molar amount of aromatic groups in the composite , lies.
  • Embodiments of the present invention will be described in the following items [1] to [25].
  • a composite material comprising a polysiloxane-containing matrix, a dispersant and dispersed particles having diameters in the ⁇ to nm range, wherein
  • Refractive index and a higher surface tension than the dispersing agent is constructed using at least two different silanes and aromatic groups and organic groups, the latter being bridged together via a bridging agent, wherein both the aromatic groups and the organic, bridgeable groups each above Carbon to a
  • the matrix additionally comprises a bridging agent having at least two reactive radicals for bridging the organobreakable groups and, if necessary, a catalyst necessary for the bridging reaction, such that the organically bridgeable groups in the cured state at least partially via an addition reaction with the bridging agent have reacted, and
  • Dispersants were mixed and the resulting mixture with the
  • polysiloxane-containing matrix was combined, with the proviso that there are no styryl groups among the aromatic groups of the composite, or that the proportion of styryl groups at less than 5 mol%, preferably less than 1 mol%, based on the total molar amount of aromatic groups in the composite , lies.
  • polysiloxane-containing matrix is at least one first silane selected from silanes having one to three, preferably two, hydrolytically condensable groups and carrying at least one, preferably two, aromatic groups attached via carbon to the silicon atom of the silane and having at least one second silane selected from silanes having one to three hydrolytically condensable groups and having at least one organic group bridgeable via a bridging agent having such an organic group of a second such silane molecule.
  • Dialkoxydiphenylsilanes trialkoxyphenylsilanes, derivatives of these silanes in which the Phenyl groups with carbon, hydrogen and optionally oxygen
  • Norbornenyl carry, Tnalkoxysilanen carrying an attached via carbon to the silicon atom of the silane epoxy, thio or amino group, and mixtures of the aforementioned silanes.
  • Bridging agent carries at least two reactive radicals selected from Si-H groups and SH groups.
  • Tnalkoxysilanes carrying a thio or amino group attached via carbon to the silicon atom of the silane, and mixtures of the aforementioned silanes, and wherein the bridging agent carries at least two reactive radicals selected from acrylic and methacrylic groups.
  • Tnalkoxysilanes which carry an attached via carbon to the silicon atom of the silane epoxy group, and wherein the bridging agent carries as reactive radicals at least two hydroxyl groups.
  • the dispersant is a polysiloxane-containing material composed of at least two hydrolytically condensable silanes, wherein the first silane is either thermally and / or light-crosslinkable organic groups or Si-H groups and the second silane bears aromatic groups.
  • (Meth) acrylic group is bonded via carbon to the silicon atom of the silane, or a mixture of two or more such (meth) acrylic silanes and the second silane is a phenyl group-containing silane.
  • Bridging agent of the polysiloxane-containing matrix are identical.
  • Diameters in the ⁇ to nm range with organic, thermally or under the action of light organically crosslinkable groups are surface-modified, which are selected so that they with the organically crosslinkable groups of the dispersant
  • polysiloxane-containing matrix is combined, whereupon the resulting composite material is cured by light and / or heat to the composite.
  • the invention is based on the finding that there are hitherto no transparent, thermally and optically stable composites of very high-indexing matrices and suitable particles with diameters in the ⁇ to nm range, since matrices, which by the way have the required properties, with the respectively desired or required particles with
  • Diameters in the ⁇ to nm range are incompatible such that the composites formed are opaque, as the inventors had to establish by comparison experiments.
  • clear, high-index matrix materials and nanoparticles can be used to
  • Dispersant can therefore be chosen a matrix with a very high refractive index and with a relatively high surface tension (a higher polarity), without this styryl-containing silanes would have to be used, which according to the invention is to be avoided because of the associated yellowing phenomena. Because of the bridging agent present in the matrix, relatively long-chain organic bridges, which prevent cracking, are formed during curing. Small impurities in styryls, the proportion of which is so low that yellowing does not occur, are harmless.
  • the polysiloxane matrix is produced by controlled hydrolysis and condensation reactions from two or more than two hydrolytically condensable silanes, especially those bearing two and / or three alkoxy groups, as known in the art.
  • the number of the hydrolytically condensable groups controls the nature of the forming inorganic network: while silanes having two such groups predominantly form chains and / or rings, the use of silanes having three such groups results in a branched network.
  • Silanes with only one hydrolytically condensable group can serve as chain terminator and therefore, according to the invention, may optionally also be used in smaller amounts.
  • the matrix according to the invention has a higher, at least before curing
  • At least one of the silanes used for this carries one or more aromatic groups, which are usually attached via carbon to the silicon atom.
  • aromatic groups contribute to a high refractive index of the resin, it being clear to the person skilled in the art that the number of these groups is responsible for the size of the refractive index increase. It is therefore preferred that the highest possible proportion of the starting silanes, e.g. up to about 70% by weight, one or preferably two such groups.
  • Aryl groups such as unsubstituted or substituted phenyl groups or fused aromatic groups, such as naphthyl or anthranyl groups, are particularly suitable as aromatic groups.
  • radicals having two or more phenyl radicals which are isolated from one another such as bisphenol A derivatives.
  • the substituents of the aromatic rings are preferably alkyl groups or other (preferably only) based on carbon, hydrogen and optionally oxygen-based groups such as polyoxyalkylene radicals.
  • the high refractive index should, according to the invention, be effected substantially or completely without the use of styryl groups, so that a substitution of phenyl groups as aromatic groups with vinyl is completely or substantially excluded.
  • the refractive index can basically be chosen freely; however, it should be as high as possible due to its intended use.
  • Favorable and achievable are values which are at least higher than the hitherto commercially available values of up to 1, 54 or 1.55.
  • the matrix has at least one prior to curing
  • aromatic silanes of the matrix are mono- or diarylsilanes, the two
  • hydrolyzable (hydrolytically condensable) groups or OH groups hydrolyzable (hydrolytically condensable) groups or OH groups.
  • a small amount of monoarylsilanes can also be added. The usage of
  • Diarylsilanes are preferred. Examples are diphenylsilanes having two hydrolyzable groups, for example dialkoxydiphenylsilanes such as dimethoxydiphenylsilane.
  • a second silane bears organic bridging groups via a bridging agent, which react with this bridging agent when the resin hardens, thereby forming relatively long-chain organic bridges.
  • silanes having organic bridging groups via a bridging agent are vinyl and allyl silanes, e.g. via Si-H groups or SH groups (by means of a thiol-ene addition) can be bridged organic.
  • Particularly suitable are vinyl and allyl silanes with three hydrolytically condensable groups such as vinyltrialkoxysilanes or allyltrialkoxysilanes, where silanes bearing two vinyl or allyl groups can also be used.
  • the vinyl or allyl group is preferably attached directly to the silicon atom.
  • these silanes are those which have, for example, (meth) acrylic groups which can also be bridged organically with Si-H groups or SH groups.
  • the bridging agent has, for example, (meth) acrylic groups
  • these silanes may be mercaptosilanes (thiosilanes). The expert can readily continue the list of possibilities on the basis of the given conditions.
  • (meth) acrylic is intended to mean “methacrylic and / or acrylic”.
  • the bridging agent used is a compound which has at least two reactive radicals which can be added to the organic bridgeable groups mentioned, or a combination of two or more of these compounds.
  • the reactive residues may be e.g. around
  • Mercapto groups act by a thiol-ene addition of (meth) acrylate or
  • Norbonen phenomenon connect to reactive hydrogen groups that can bind to an allyl or vinyl group, or to hydroxy groups that can bind to an epoxy group.
  • the bridging agent also carries aromatic groups in order to avoid "dilution" of these groups in the matrix by the addition of the bridging agent If the bridging agent has more than two, for example three reactive radicals, it can have a crosslinking effect.
  • a bridging agent can, but need not, also a silane compound can be used. If these are to have reactive hydrogen groups, these may be Si-H groups. Alternatively, it may be, for example, a thiosilane whose thio group is bonded to a silyl radical which is bonded to the silicon via carbon. Particularly suitable is a compound which carries two silicon atoms with active groups, for example Si-H groups. These two silicon atoms can be linked together via a diphenylene ether bridge. A concrete example is bis [(p-dimethylsilyl) phenyl] ether).
  • Bridging agent increases the total number of reactive groups. It is favorable, e.g. the addition of a bridging agent having two reactive groups, for example Si-H groups, in such amount to the silane, the bridgeable groups, e.g. Vinyl groups, that the ratio of the reactive groups of the bridging agent to the number of
  • bridgeable groups on the silane is stoichiometric. Because this increases the number of bridgeable groups to double. It is particularly advantageous if the atomic chain has as many members as possible between at least two of the reactive radicals of the bridging agent, because the bridging then leads to a relatively wide-meshed network, although again it should be noted that long aliphatic chains lower the refractive index. However, this does not apply to more extended aromatic chains whose aromatic components need not necessarily be conjugated.
  • the chain (calculated without the reactive radicals) between the two reactive radicals should, based on the above considerations, preferably at least 6, more preferably at least 8 chain links, for any rings such as phenyl rings, the shortest distance is expected between the two binding sites of the rings lies. For p-phenyl structures, for example, these are 4 (carbon) atoms.
  • the ratio of aromatic group-containing silanes to organic bridgeable groups is basically not critical, as long as a sufficient amount of aromatic groups is present, so that the desired, high refractive index is achieved. Of course, the highest possible proportion of aromatic groups is favorable.
  • the refractive index should be as high as possible, but at the same time it must be ensured that a sufficient proportion of organically bridgeable groups is present, with the aid of which the resin can be cured, it is advantageous to use the aromatic-containing silane in a molar proportion, Based on the sum of aromatic groups and organic bridgeable groups, use of up to about 80%, but under certain circumstances this proportion can even rise to about 95%, preferably up to about 90% (for example, the proportion is a use of 30 mol% vinyltrialkoxysilane and 70 mol% dialkoxydiphenylsilane at ca. 82 mol%).
  • the crosslinking agent should in turn one contain as high a proportion of aromatic groups in order to give the matrix the desired high refractive index.
  • Poly reaction can be crosslinked by heat or light, such as silanes containing (meth) acrylate groups, because this may be another
  • silanes can be used which contain one (or more) longer chain alkyl group, which reduces the brittleness of the later composite and increases the flexibility of the network.
  • the resin matrix is preferably prepared by jointly subjecting the two different silanes, which carry organic crosslinkable groups or aromatic groups via a bridging agent, to a hydrolytic condensation reaction.
  • the silanes are mixed, which is usually possible without the addition of solvent, since the starting components are usually liquid.
  • the mixture becomes a hydrolysis and subjected to condensation, for example, with a substoichiometric to stoichiometric amount of water, based on the existing hydrolytic
  • condensable radicals and optionally a catalyst, e.g. Acid such as hydrochloric acid, can be effected.
  • a catalyst e.g. Acid such as hydrochloric acid
  • the compounds liberated in the condensation, such as e.g. Ethanol or methanol are then removed along with the excess water, and preferably the catalyst, which may be effected by extraction with an extractant and / or by stripping off (distilling) volatile components.
  • the resulting inorganic condensate is a storable resin. Should it be with the rest
  • Components are processed to composite according to the invention, are the
  • Crosslinking agent and, if necessary, added a corresponding catalyst.
  • the dispersant is needed to incorporate the particles into the high refractive index matrix.
  • the dispersant should also be as high-index as possible, without contributing to a yellowing of the layer.
  • aromatic groups which may be selected from the same group of aromatics, for example, arylene, as indicated above for the matrix.
  • aryl-containing silanes are the source for this.
  • the dispersant should additionally be organically crosslinkable or it should allow organic bridging.
  • organic crosslinkability can be selected with regard to the particles to be used, but also either a crosslinkability of the crosslinkable groups chosen for the dispersant with one another and / or a crosslinkability with a
  • Component of the matrix can be envisaged.
  • crosslinkable groups are selected with regard to the particles to be used, it may be advantageous to use crosslinkable groups which polymerize organically thermally and / or under the action of light. For example, if particles are used whose surface is also occupied by organically polymerizable groups, these particles can be added to the corresponding components of the above-mentioned groups
  • crosslinkable groups and / or a crosslinkability with a component of the matrix is possible, for example, if groups are used which can be thermally and / or with the aid of light polymerization (English: "addition polymerization") subjected.
  • the crosslinkable groups are preferably provided via silanes, which in a first embodiment of the invention are hydrolytic Condensation reaction are subjected. For the connection of these groups to the
  • Silicon atoms are similar to those described above for the matrix resin.
  • a (meth) acrylate-based polycondensate is selected as the dispersant, ie a polycondensate with thermal and / or organic action under the action of light
  • polymerizable groups These groups can be introduced via silanes which contain these groups on radicals attached to the silicon via carbon.
  • the aromatic groups of the dispersant can also be silanes
  • silanes of a hydrolytic co-condensation can be subjected.
  • These silanes may, for example, have two or three hydrolytically condensable groups and one or two aryl groups, the latter also being bonded to the silicon via carbon.
  • the dispersant is chosen to be an organic compound
  • This dispersant is referred to as a molecular dispersant, as opposed to the polycondensed dispersant described above.
  • the bridging agent of the matrix resin Like the bridging agent of the matrix resin, it carries two reactive groups and may be selected from the same group of compounds as the bridging agent. Optionally, it may be identical to the bridging agent.
  • vinyl-functionalized matrix resin can be selected from a silane compound containing at least two Si-H groups, which is first brought into contact with the nanoparticles and then with the resin and leads to crosslinking and curing of the composite.
  • This silane compound may optionally itself have aromatic groups, for example aryl groups, or it may be combined with other aromatic-containing silanes.
  • the dispersant has an adapted polarity in order to distinguish between the possibly
  • the amount in which it is to be used is not limited; however, it should be sufficient to cover the particles with diameters in the ⁇ to nm range.
  • the term "wrapping" is intended to mean that the polarity is thereby optimized so far that a compatibility and miscibility is given. This does not mean, however, that complete encapsulation in the sense of blanket coverage of the surface of the nanoparticles and steric shielding is mandatory, although it will be achieved frequently.
  • the proportion of dispersing agent, based on the sum of matrix and dispersing agent can therefore vary between 1 and 99% by weight; in the As a rule, about 10 to 50% by weight, based on the stated sum of matrix and dispersant, will be used.
  • Polycondensates of the matrix or the dispersant have only slightly different polarity, based on the surface tension.
  • the particles of the invention in the dispersed state have diameters in the ⁇ to nm range. If they are to serve the increase in refractive index, this diameter is below the wavelength of the light, for the passage of which the composite according to the invention is provided, and thus between about 400 nm to about 800 nm on average. These particles are also referred to as nanoparticles. If the particles are intended for the conversion of light, as explained in more detail below, the diameter may also be above 800 nm and e.g. optionally also reach about 50 ⁇ .
  • Breakage-increasing nanoparticles can be commercially available, preferably functionalized on the surface with a wide variety of groups, or else according to typical methods
  • nanoparticles are used.
  • the nanoparticles are preferably made of metal oxides or nitrides, for example those of zirconium or titanium. They are preferably present in dispersion.
  • Functionalization may, but need not, be in one or more organically polymerizable groups that can be applied via silanization. Preference is given to organically crosslinkable or polymerizable groups which can copolymerize with the corresponding organically crosslinkable groups of the dispersant.
  • particles can be used with which the color of an LED can be specifically changed.
  • the composite is not or not only used to encapsulate the LED; rather, the layer containing or consisting of the composite (only or in addition) serves as so-called
  • Conversion layer contains particles or nanoscale substances that absorb the light emitted by the LED, short-wave, high-energy and thus perceived as "cold” and re-emit the energy absorbed in the form of light of longer wavelengths (for example yellow).
  • the light emerging from the LED (in the case of eg InGaN or GaN as semiconducting material usually blue or even emitting in the UV range) is sent in this technique through the conversion layer, which rests either directly on the LED chip or a certain distance owns (the latter is called "remote phosphor").
  • the layer can simultaneously serve as an encapsulation layer.
  • the light rays emerging from the conversion layer in the sum then lead to a white light impression.
  • converter substances are common
  • phosphors Semiconductor materials used. When it comes to particulate substances (phosphors), these often have diameters in the ⁇ scale, for example 1 -50 ⁇ , which are used as a powder.
  • An example (which is not to be considered as limiting) is yttrium-aluminum-garnet Y 3 Al 5 O 12: Ce doped with cerium, a material from the group having the general form A 3 B 5 X 12 : M, in which there are further phosphors gives.
  • nanoscale conversion materials nanoparticles
  • quantum dots can be used, which are also called quantum dots.
  • CdSe which, however, has recently received competition from Cd-free materials such as InP or InP / ZnS, as well as other sulfides such as PbS and ZnS due to the toxicity of cadmium.
  • Cd-free materials such as InP or InP / ZnS
  • PbS and ZnS sulfides
  • These converter materials generally have the goal of improving or changing the performance, efficiency and color value of the LED.
  • An essential challenge is the adequate stabilization and distribution of the converter materials in a corresponding matrix. Above all, it must be avoided that the phosphors on the bottom of the applied layer agglomerate and accumulate there before the layer has hardened, in order to prevent shifts in the layers
  • the composite according to the invention is prepared by mixing the dispersant and the nanoparticles together, both components being used if necessary dissolved in a suitable solvent.
  • the solvent is then removed, for example by distillation and optionally subsequent application of heat and reduced pressure.
  • the resin of the matrix and the dispersant mixed with the nanoparticles are mixed. If no catalyst for the bridging reaction was incorporated into the matrix resin, but this is required, this catalyst is added to the mixture.
  • a dispersant is proposed as a supplementary component for a translucent, clear, yellowing-resistant and high-index composite.
  • composites can be obtained which, after curing, have refractive indices of more than 1.6, preferably more than 1.65.
  • refractive indices of more than 1.6, preferably more than 1.65.
  • particle systems The particles used in the examples had a particle diameter (DLS, volume weighted, including functionalization shell) of about 5 to 8.3 nm. They had a core of ZrO 2 with an acrylate and / or methacrylate-modified surface. Their refractive index (including functionalization shell) was in all cases about 1, 8. They were used in the form of a 50% suspension in PGMEA (1-methoxy-2-propyl acetate).
  • the mixture reacts for 24 h at 80 ° C in an oil bath.
  • the resin thus obtained is subsequently purified by means of a hydrophobic filter and the remaining volatile constituents are removed by distillation.
  • the refractive index of the resin thus obtained is 1, 5795 (598 nm, 20 ° C, Abbe refractometer).
  • the molar mass of the Si-H compound of 286.52 g / mol gives, at 0.589 g, a molar mass of 2.06 mmol.
  • the molar ratio of vinyl to diphenyl component is 1: 2, resulting in a mass concentration of 16.6 wt .-% for the hydrolyzed and condensed vinyl component in the resin. That is, 2.0 g of resin contains 0.332 g of the hydrolyzed and condensed vinyl component.
  • the resulting resin is then purified by means of a hydrophobic filter and the remaining volatiles are removed by distillation.
  • the refractive index of the resulting resin is 1.5681 (598 nm, 20 ° C) and the surface tension is 35.6 mN / m. Despite the relatively small difference in surface tension, this causes
  • Dispersing agent that the Zr0 2 nanoparticles used can be optimally dispersed and an agglomeration-free, transparent layer can be produced.
  • the refractive index of the cured layer is 1.583 (635 nm, prism coupler).
  • a first step 2.08 g of dispersant (see Example 3) are dissolved in 50 ml of 1-methoxy-2-propyl acetate in a 250 ml round bottom flask. 8.91 g of a 50% strength by weight solution of surface-functionalized ZrO 2 nanoparticles in 1-methoxy-2-propyl acetate are added to this solution. The mixture is treated for 30 minutes in an ultrasonic bath. Subsequently, the solvent is removed by distillation. Last remnants of the volatiles are removed in a vacuum oven at 60 ° C and so the dispersed
  • Dispersant to resin is 2.1: 1, and the composite mixture stirred for four hours at room temperature. Subsequently, the addition of 0.1 wt .-% is carried out
  • the subsequent curing of thin layers of this composite can be carried out by a three-stage oven treatment at eg first 100 ° C for two hours, 150 ° C for one hour and finally 180 ° C for another hour.
  • the refractive index of the ZrO 2 -containing composite with the aid of a polycondensed dispersant is 1 .650 (635 nm prism coupler measurement on cured samples).
  • the subsequent curing of thin layers of this composite is carried out at 100 ° C for 7 h in the oven.
  • the refractive index of the thus-obtained ZrO 2 -containing composite layers by means of a molecular dispersant having SiH groups is 1.635 (635 nm - prism coupler measurement of the cured layer).
  • the refractive index of layers of the pure resin is 1.597 (635 nm, prism coupler) in this measurement method. Comparative example without dispersant
  • Composite cross-sections show enhanced agglomeration of the Zr0 2 nanoparticles.
  • the size of the resulting agglomerates is between about 400 nm and several 10 ⁇ and is thus in the range of scattering particles.
  • Reaction mixture is the solvent 1 -methoxy-2-2propylacetat removed by distillation to a residual solvent content of about 4 wt .-% and a thermal radical initiator dicumyl peroxide with a content of 0.3 weight percent based on the
  • the refractive index of the composite mixture thus prepared was 1.6034 (598 nm, 20 ° C, Abbe refractometer).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)
  • Led Device Packages (AREA)

Abstract

L'invention concerne un matériau composite comprenant une matrice à base de polysiloxane, un agent de dispersion ainsi que des particules dispersées ayant des diamètres de l'ordre du micromètre au nanomètre, dans lequel (a) la matrice à base de polysiloxane possède, à l'état non durci, un indice de réfraction plus élevé et une tension superficielle plus élevée que ceux de l'agent de dispersion, est conçue en utilisant au moins deux silanes différents et présente des groupes aromatiques ainsi que des groupes organiques, ces derniers pouvant être pontés les uns aux autres par l'intermédiaire d'un agent pontant, aussi bien les groupes aromatiques que les groupes organiques pouvant être pontés étant liés respectivement par du carbone à un atome de silicium. La matrice présente en outre un agent pontant ayant au moins deux radicaux réactifs pour ponter les groupes organiques pouvant être pontés et si nécessaire, un catalyseur indispensable à la réaction de pontage, de telle manière que les groupes organiques pouvant être pontés, à l'état durci, réagissent au moins en partie par une réaction d'addition avec l'agent pontant ; et (b) l'agent de dispersion présente des groupes organiques ou des groupes Si-H- réticulables soit thermiquement soit par exposition à la lumière, ainsi que (ii) des groupes aromatiques, les particules ayant des diamètres de l'ordre du micromètre au nanomètre étant d'abord mélangées à l'agent de dispersion puis le mélange obtenu étant associé à la matrice à base de polysiloxane à condition que parmi les groupes aromatiques du composite, il n'y ait pas de groupes styryle ou que la fraction de groupes styryle représente moins de 5 % en moles, de préférence moins de 1 % en moles, rapporté à la quantité molaire totale des groupes aromatiques dans le composite. L'invention concerne également un composite fabriqué par durcissement à partir de ce matériau. L'invention concerne par ailleurs un procédé pour fabriquer le matériau composite et le composite.
EP17713175.2A 2016-03-15 2017-03-08 Matériaux pour encapsulation de del Active EP3430085B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016104790.2A DE102016104790A1 (de) 2016-03-15 2016-03-15 Materialien für die LED-Verkapselung
PCT/EP2017/055479 WO2017157743A1 (fr) 2016-03-15 2017-03-08 Matériaux pour encapsulation de del

Publications (2)

Publication Number Publication Date
EP3430085A1 true EP3430085A1 (fr) 2019-01-23
EP3430085B1 EP3430085B1 (fr) 2020-06-24

Family

ID=58410251

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17713175.2A Active EP3430085B1 (fr) 2016-03-15 2017-03-08 Matériaux pour encapsulation de del

Country Status (6)

Country Link
US (1) US20190088838A1 (fr)
EP (1) EP3430085B1 (fr)
JP (1) JP2019508565A (fr)
CN (1) CN108779334A (fr)
DE (1) DE102016104790A1 (fr)
WO (1) WO2017157743A1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107154422B (zh) * 2017-05-12 2019-11-15 武汉华星光电技术有限公司 一种柔性有机发光二极管显示器及其制作方法
TWI798343B (zh) * 2018-03-12 2023-04-11 美商陶氏有機矽公司 可固化聚矽氧組成物及其經固化產物
DE102019107765A1 (de) * 2019-03-26 2020-10-01 OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung Lebenszeichensensor und verfahren zur herstellung eines lebenszeichensensors
CN110845989B (zh) * 2019-12-02 2021-09-03 苏州太湖电工新材料股份有限公司 一种双组份有机硅灌封胶及其应用方法
CN115594946B (zh) * 2022-10-28 2024-06-04 江苏鸿佳电子科技有限公司 一种led封装用复合材料及其制备方法

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19964252A1 (de) 1999-12-30 2002-06-06 Osram Opto Semiconductors Gmbh Oberflächenmontierbares Bauelement für eine LED-Weißlichtquelle
US7192795B2 (en) 2004-11-18 2007-03-20 3M Innovative Properties Company Method of making light emitting device with silicon-containing encapsulant
JP5167582B2 (ja) * 2005-10-28 2013-03-21 住友大阪セメント株式会社 ジルコニア透明分散液及び透明複合体並びに透明複合体の製造方法
WO2007049573A1 (fr) 2005-10-28 2007-05-03 Sumitomo Osaka Cement Co., Ltd. Dispersion transparente d’oxyde inorganique, composition de resine contenant des particules d’oxyde inorganique, composition pour encapsuler un element luminescent, element luminescent, revetement dur, film fonctionnel optique, piece optique et procede de production d’une composition de resine contenant de
JP2009024116A (ja) * 2007-07-23 2009-02-05 Sony Corp 硬化性樹脂材料−微粒子複合材料及びその製造方法、光学材料、並びに発光装置
JP2009024117A (ja) * 2007-07-23 2009-02-05 Sony Corp 硬化性樹脂材料−微粒子複合材料及びその製造方法、光学材料、並びに発光装置
JP5393107B2 (ja) * 2007-12-25 2014-01-22 日東電工株式会社 シリコーン樹脂組成物
KR100980270B1 (ko) 2008-07-31 2010-09-07 한국과학기술원 Ｌｅｄ 봉지용 실록산 수지
US8329290B2 (en) * 2008-12-22 2012-12-11 Nitto Denko Corporation Silicone resin composition
KR101259887B1 (ko) * 2009-08-04 2013-05-02 한국과학기술원 광학용 투명 실록산 수지 조성물
JP5549568B2 (ja) * 2009-12-15 2014-07-16 信越化学工業株式会社 光半導体素子封止用樹脂組成物及び当該組成物で封止した光半導体装置
CN103370361B (zh) 2011-01-21 2017-07-18 弗劳恩霍弗应用技术研究院 可聚合组合物、由其得到的固化产物以及这些材料的用途
JP5795949B2 (ja) * 2011-11-25 2015-10-14 第一工業製薬株式会社 光学材料用樹脂組成物
CN102751447B (zh) * 2012-07-04 2015-08-12 信利半导体有限公司 光学过渡层材料、光学基板/封装层、oled及各自制法
JP2014062198A (ja) * 2012-09-21 2014-04-10 Dow Corning Toray Co Ltd 硬化性シリコーン組成物、それを用いてなる半導体封止材および光半導体装置
JP5931767B2 (ja) * 2013-02-01 2016-06-08 信越化学工業株式会社 光反射材料用硬化性樹脂組成物、該組成物の硬化物、該組成物の硬化物からなるリフレクター及びこれを用いた光半導体デバイス
JP6928557B2 (ja) * 2015-03-30 2021-09-01 ピクセリジェント・テクノロジーズ，エルエルシー 高屈折率で無溶剤のシリコーンナノ複合材料

Also Published As

Publication number Publication date
WO2017157743A1 (fr) 2017-09-21
US20190088838A1 (en) 2019-03-21
EP3430085B1 (fr) 2020-06-24
CN108779334A (zh) 2018-11-09
JP2019508565A (ja) 2019-03-28
DE102016104790A1 (de) 2017-09-21

Similar Documents

Publication Publication Date Title
EP3430085B1 (fr) Matériaux pour encapsulation de del
DE69920821T2 (de) Anorganisch-organisches Hybrid-Polymermaterial mit Zusammensetzungsgradient und Verfahren zu dessen Herstellung
EP1463963A1 (fr) Procede de production d'elements optiques ayant une structure en gradient
KR101496409B1 (ko) 무기 산화물 입자와 실리콘 수지의 복합 조성물 및 그 제조 방법, 및 투명 복합체 및 그 제조 방법
DE602004006610T2 (de) Optisch transparente, temperaturbeständige polysiloxane mit hohem brechungsindex
DE112013003864B4 (de) Transparente Schichtstruktur und Verfahren zum Herstellen derselben
JP5780003B2 (ja) 無機酸化物粒子とシリコーン樹脂との複合組成物及び透明複合体
EP2943826A2 (fr) Couches ou corps moulés tridimensionnels comportant deux zones de structures primaires et/ou secondaires différentes, procédé de production du corps moulé et matériaux pour la mise en oeuvre de ce procédé
EP0587667A1 (fr) Compositions d'enduction a base de polycondenses anorganiques fluores, leur preparation et leur utilisation.
JP5072820B2 (ja) シリコーン樹脂組成物
EP1465946A1 (fr) Matiere nanocomposite pour la fabrication de feuilles a gradient d'indice de refraction
EP1195416A2 (fr) Nanocapsules organosiliciés polymérisables
KR20160148626A (ko) 매트릭스 부재 중합체 나노복합체 및 그의 관련 제품 및 방법
EP3390274A1 (fr) Élément de conversion, composant opto-électronique le comprenant et procédé de fabrication d'un élément de conversion
DE112020000730T5 (de) Fusionierte Verkapselung von Quantenpunkten
EP3774998A1 (fr) Matériaux composites nanostructurés présentant des propriétés autocicatrisantes
WO2013153003A1 (fr) Composant émetteur de rayonnement, matériau transparent et particule de charge ainsi que procédé pour leur fabrication
DE102012106984A1 (de) Optoelektronisches Halbleiterbauelement und Verfahren zur Herstellung eines optoelektronischen Halbleiterbauelements
TWI496827B (zh) Silicon oxide resin compositions for light semiconductors and their hardened products
DE102021118751A1 (de) Aushärtbare silikonzusammensetzung, einkapselungsmittel und optische halbleitervorrichtung
WO2018054992A1 (fr) Procédé de fabrication d'un élément de sortie destiné à un composant optoélectronique et élément de sortie
WO2017144680A1 (fr) Composant optoélectronique et procédé de fabrication d'un composant optoélectronique
JP5769154B2 (ja) 無機酸化物粒子とシリコーン樹脂との複合組成物ならびに透明複合体およびその製造方法
DE102007009557A1 (de) Verfahren zur Herstellung einer mehrlagigen optischen Wellenleiterstruktur und mehrlagige optische Wellenleiterstruktur
US20210024719A1 (en) Photocurable composition, a hydrogel and a molded product thereof

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20181001

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: FRAUNHOFER GESELLSCHAFT ZUR FOERDERUNG DER ANGEWAN

Owner name: OSRAM OPTO SEMICONDUCTORS GMBH

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200204

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1283865

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200715

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502017005857

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200925

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200924

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200924

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201026

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20201024

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502017005857

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20210325

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20210308

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20210331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210308

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210331

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210308

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210331

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210308

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210331

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 1283865

Country of ref document: AT

Kind code of ref document: T

Effective date: 20220308

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230617

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20170308

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220308

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200624

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20240321

Year of fee payment: 8